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Volcanic plumes are sites of dynamic chemistry involving halogen gases. Here we present new data on the relative abundances of SO2, BrO and OClO gases emitted from Soufrière Hills Volcano [SHV). They were collected during an eruptive hiatus but during sustained degassing at this halogen-rich volcano. By comparison with data from a previous study during an eruptive phase and application of the data and modeling of Villemant et al. (2008), we suggest that, after consideration of errors, either the rate of HBr conversion to BrO is variable, ranging from ∼30% to ∼15%, and/or the relative partitioning of Cl and Br into the gas phase from the melt changes according to eruptive activity. We examine the potential implications of this for fluid-melt partitioning, and compare our results with data from the experimental literature. Our work contributes toward understanding the controls on the BrO/SO2 ratio for volcano monitoring purposes; the changes in plume chemistry with regard to bromine at the onset of lava extrusion may be large and rapid. OClO was detected in the plume at SHV for the first time. This species has only previously been detected in emissions from Mount Etna (using ground-based methods) and from Puyehue Cordon Caulle (using satellite-based methods). No HCHO or NOy species were detected in the spectra.

[1] Direct-sampling and remote-sensing measurements were made at the crater rim of Masaya volcano (Nicaragua) to sample the aerosol plume emanating from the active vent. We report the first measurements of the size distribution of fine silicate particles (d < 10 μm) in Masaya's plume, by automated scanning electron microscopy (QEMSCAN) analysis of a particle filter. The particle size distribution was approximately lognormal with modal d ∼ 1.15 μm. The majority of these particles were found to be spherical. These particles are interpreted to be droplets of quenched magma produced by a spattering process. Compositional analyses confirm earlier reports that the fine silicate particles show a range of compositions between that of the degassing magma and nearly pure silica and that the extent of compositional variability decreases with increasing particle size. These results indicate that fine silicate particles are altered owing to reactions with acidic droplets in the plume. The emission flux of fine silicate particles was estimated as ∼1011 s-1, equivalent to ∼55 kg d-1. Sun photometry, aerosol spectrometry, and thermal precipitation were used to determine the overall particle size distribution of the plume (0.01 < d(μm) < 10). Sun photometry and aerosol spectrometry measurements indicate the presence of a large number of particles (assumed to be aqueous) with d ∼ 1 μm. Aerosol spectrometry measurements further show an increase in particle size as the nighttime approached. The emission flux of particles from Masaya was estimated as ∼1017 s-1, equivalent to ∼5.5 Mg d-1 where d < 4 μm. Copyright 2009 by the American Geophysical Union.

We report measurements of Hg, SO2, and halogens (HCl, HBr, HI) in volcanic gases from Masaya volcano, Nicaragua, and gaseous SO2 and halogens from Telica volcano, Nicaragua. Mercury measurements were made with a Lumex 915+ portable mercury vapor analyzer and gold traps, while halogens, CO2 and S species were monitored with a portable multi gas sensor and filter packs. Lumex Hg concentrations in the plume were consistently above background and ranged up to 350 ng m-3. Hg/SO2 mass ratios measured with the real-time instruments ranged from 1.1 × 10-7 to 3.5 × 10-5 (mean 2 × 10-5). Total gaseous mercury (TGM) concentrations measured by gold trap ranged from 100 to 225 ng m-3. Reactive gaseous mercury accounted for 1% of TGM, while particulate mercury was 5% of the TGM. Field measurements of Masaya's SO2 flux, combined with the Hg/SO2 ratio, indicate a Hg flux from Masaya of 7.2 Mg a-1. At Masaya's low temperature famaroles, Hg/CO2 mass ratios were consistently around 2 × 10-8, lower than observed in the main vent (Hg/C02 ∼ 10-7). Low-temperature fumarole Hg fluxes from Masaya are insignificant (∼150 g a-1). Ratios of S, C and halogen species were also measured at Masaya and Telica volcanoes. CO2/ SO2 ratios at Masaya ranged from 2.8 to 3.9, comparable to previously published values. At Masaya molar Br/SO2 was 3 × 10-4 and I/SO2 was 2 × 10-5, suggesting fluxes of 0.2-0.5 Mg HBr d-1 and 0.02-0.05 Mg HI d-1. At Telica the Br/SO2 ratio was also 3 × 10-4 and the I/SO2 ratio was 5.8 × 10-5, with corresponding fluxes of 0.2 Mg HBr d-1 and 0.06 Mg HI d-1. Gases at both volcanoes are enriched in I relative to Br and Cl, compared to gases from volcanoes elsewhere. Copyright 2008 by the American Geophysical Union.

Here we report results from a multidisciplinary field campaign at Villarrica volcano, Chile, in March 2009. A range of direct sampling and remote sensing techniques was employed to assess gas and aerosol emissions from the volcano, and extend the time series of measurements that have been made during recent years. Airborne traverses beneath the plume with an ultraviolet spectrometer yielded an average SO2 flux of 3.7kg s-1. This value is similar to previous measurements made at Villarrica during periods of quiescent activity. The composition of the plume was measured at the crater rim using electrochemical sensors and, for the first time, open-path Fourier transform infrared spectroscopy, yielding a composition of 90.5mol% H2O, 5.7% CO2, 2.6% SO2, 0.9% HCl, 0.3% HF and

Near-source observations of aerosol size distributions ( 1 [mu]m) ash particles. The number ratio of fine and coarse particles fluctuated strongly within short intervals of time, indicative of changes in the fragmentation energy. The near-source ash fallout was poorly sorted (interquartile range 16-80 [mu]m); ash grains sized

International audience; The measurement of SO2 flux from volcanoes is of major importance for monitoring and hazard assessment purposes, and for evaluation of the environmental impact of volcanic emissions. We propose here a novel technique for accurate and high time resolution estimations of the gas flux. We use two wide field of view UV spectrometers capable of collecting, instantaneously, light from thin parallel cross sections of the whole gas plume, obviating the need for either traversing, scanning or imaging. It enables tracking of inho-mogeneities in the gas cloud from which accurate evaluation of the plume velocity can be made by correlation analysis. The method has been successfully applied on Mt. Erebus volcano (Antarctica). It yields estimations of the plume velocity and gas flux at unprecedented time resolution (1 Hz) and high accuracy (uncertainty of 33%). During a ∼2 h experiment on 26 December 2006, SO2 flux varied between 0.17 and 0.89 ± 0.2 kg s −1 with a vertical plume velocity varying between 1 and 2.5 ± 0.1 m s −1. These measurements provide insight into the short-term variations of the passive degassing of this volcano renowned for its active lava lake. A cyclicity in flux, ranging from about 11-24 min, is evident. We propose two physical mechanisms to explain this degassing pattern, associated to periodic supply of either gas-rich magma or gas alone into the lake. The dual-wide field of view DOAS technique promises better integration of geochemical and geophysical observations and new insights into gas and magma dynamics, as well as processes of magma storage and gas segregation at active volcanoes.

Here we report measurements of the chemical composition and flux of gas emitted from the central lava lake at Erta 'Ale volcano (Ethiopia) made on 15 October 2005. We determined an average SO 2 flux of ∼ 0.69 ± 0.17 kg s − 1 using zenith sky ultraviolet spectroscopy of the plume, and molar proportions of magmatic H 2 O, CO 2 , SO 2 , CO, HCl and HF gases to be 93.58, 3.66, 2.47, 0.06, 0.19 and 0.04%, respectively, by open-path Fourier transform infrared (FTIR) spectrometry. Together, these data imply fluxes of 7.3, 0.7, 0.008, 0.03 and 0.004 kg s − 1 for H 2 O, CO 2 , CO, HCl and HF, respectively. These are the first FTIR spectroscopic observations at Erta 'Ale, and are also some of the very few gas measurements made at the volcano since the early 1970s (Gerlach, T.M., 1980b. Investigation of volcanic gas analyses and magma outgassing from Erta 'Ale lava lake, Afar, Ethiopia. Journal of Volcanology and Geothermal Research, 7(3–4): 415–441). We identify significant increases in the proportion of H 2 O in the plume with respect to both CO 2 and SO 2 across this 30-year interval, which we attribute to the depletion of volatiles in magma that sourced effusive eruptions during the early 1970s and/or to fractional magma degassing between the two active pit craters located in the summit caldera.

We report here the first observations of NO2 emission from Mt. Erebus, a volcano with an active lava lake located on Ross Island, Antarctica. Erebus generates a persistent plume, which is entrained at an altitude of about 4 km above sea level. Its NO2 flux, measured by scattered light ultraviolet spectroscopy in December 2003, was equivalent to ∼0.6 Gg (N) yr-1. The total reactive nitrogen supply may be significantly higher than this since other NOy species are likely to have been present in the plume. We believe the NO2 is generated by thermal fixation of atmospheric nitrogen at the hot lava surface, forming NO, which then reacts rapidly with oxidants including ozone to yield NO2. Erebus volcano has displayed lava lake activity for many decades and may, therefore, play a significant long-term role in Antarctic tropospheric chemistry, and represent an important source of nitrogen deposited to the ice surface. © 2005 Elsevier Ltd. All rights reserved.

Emissions of SO 2 and NO 2 from fossil fuel power stations can have serious environmental consequences via conversion to sulphuric and nitric acids and subsequent deposition. Consequently, there is considerable interest in techniques capable of monitoring these emissions, in order to ensure compliance with environmental legislation. Here we present a novel approach to measuring power station SO 2 and NO 2 emissions by traversing underneath the plume by car or on-foot or scanning the power station's plume from a fixed position with a compact and lightweight UV spectrometer. This work was performed at a power station in eastern England during January, February and June 2003, resulting in a SO 2 flux of 5.2 kg s −1 , which is in close correspondence with the in-stack measured value of 5.3 kg s −1 . This technique is considerably simpler and cheaper than other remote sensing approaches to monitoring these emissions.

Since the first detection of bromine monoxide in volcanic plumes attention has focused on the atmospheric synthesis and impact of volcanogenic reactive halogens. We report here new measurements of BrO in the volcanic plume emitted from Kīlauea volcano – the first time reactive halogens have been observed in emissions from a hotspot volcano. Observations were carried out by ground-based Differential Optical Absorption Spectroscopy in 2007 and 2008 at Pu'u' O ' o crater, and at the 2008 magmatic vent that opened within Halema'uma'u crater. BrO was readily detected in the Halema'uma'u plume (average column amount of 3×10 15 molec cm −2 ) and its abundance was strongly correlated with that of SO 2 . However, anticorrelation between NO 2 and SO 2 (and BrO) abundances in the same plume strongly suggest an active role of NO x in reactive halogen chemistry. The calculated SO 2 /BrO molar ratio of ~1600 is comparable to observations at other volcanoes, although the BrO mixing ratio is roughly double that observed elsewhere. While BrO was not observed in the Pu'u' O ' o plume this was probably merely a result of the detection limit of our measurements and based on understanding of the Summit and East Rift magmatic system we expect reactive halogens to be formed also in the Pu'u' O ' o emissions. If this is correct then based on the long term SO 2 flux from Pu'u' O ' o we calculate that Kīlauea emits ~480 Mg yr −1 of reactive bromine and may thus represent an important source to the tropical Pacific troposphere.

[1] We report the first combined measurements of the composition and flux of gas emitted from Nyiragongo volcano by ground-based remote-sensing techniques. Ultraviolet spectroscopic measurements made in May/June 2005 and January 2006 indicate average SO(2) emission rates of 38 kg s(-1) and 23 kg s(-1), respectively. Open-path Fourier transform infrared spectroscopic measurements obtained in May/June 2005, January 2006, and June 2007 indicate average molar proportions of 70, 24, 4.6, 0.87, 0.26, 0.11, and 0.0016% for H(2)O, CO(2), SO(2), CO, HCl, HF, and OCS, respectively. The composition of the plume was remarkably similar in 2005, 2006, and 2007, with little temporal variation in proportions of CO(2), SO(2), and CO, in particular, on the scale of seconds or days or even between the three field campaigns that span a period of 24 months. This stability persisted despite a wide range of degassing behaviors on the surface of the summit crater's lava lake ( including discrete strombolian bursts and lava fountains) and variations in the SO(2) emission rate. We explain these observations by a regime of steady state degassing in which bubbles nucleate and ascend in chemical equilibrium with the convecting magma. Short-term ( seconds to minutes) temporal fluctuations in the SO(2)-HCl-HF composition were observed, and these are attributed to shallow degassing processes.

The explosions and subsequent fire at the Buncefield oil depot in December 2005 afforded a rare opportunity to study the atmospheric consequences of a major oil fire at close range, using ground-based remote-sensing instruments. Near-source measurements (less than 10 km) suggest that plume particles were approximately 50% black carbon (BC) with refractive index 1.73−0.42i, effective radius ( R eff ) 0.45–0.85 μm and mass loading approximately 2000 μg m −3 . About 50 km downwind, particles were approximately 60–75% BC with refractive index between 1.80−0.52i and 1.89−0.69i, R eff ∼1.0 μm and mass loadings 320–780 μg m −3 . Number distributions were almost all monomodal with peak at r 2 (70 ppbv), NO 2 (140 ppbv), HONO (20 ppbv), HCHO (160 ppbv) and CS 2 (40 ppbv). Our measurements are consistent with others of the Buncefield plume, and with studies of the 1991 Kuwaiti oil-fire plumes; differences from the latter reflecting in part contrasts in combustion efficiency and source composition (refined fuels versus crude oils) leading to important potential differences in atmospheric impacts. Other measurements made as the plume passed overhead approximately 50 km downwind showed a reduced solar flux reaching the surface, but little effect on the atmospheric potential gradient (electric field). The wind speed data from the day of the explosion hint at a possible explosion signature.

The Central American volcanic arc supplies a significant proportion of the persistent annual global sulphur dioxide emissions from volcanoes. In November/December 2003, we completed a survey of the arc section from Mombacho to San Cristobal in Nicaragua recording individual mean fluxes of 800, 530 and 220 Mg day � 1 in the plumes from San Cristobal, Telica and Masaya, respectively. An assessment of fluxes published since 1997 along the entire Central America arc yields a mean total arc flux of SO2 of 4360 Mg day � 1 or 8-16% of the annual estimated global volcanic SO2 flux to the troposphere. New field data shows that Masaya volcano continues to show stable HCl/SO2 and HF/SO2 ratios, suggesting a sustained flux of these components of ~220 and 30 Mg day � 1 , respectively (1997 to 2004). Masaya's plume composition also appears to have been stable, between 2001 and 2003, with respect to all the particulate species measured, with significant fluxes of SO4 2� (4 Mg day � 1 ), Na + (0.9-1.3 Mg day � 1 ) and K + (0.7 Mg day � 1 ). Extrapolating the Masaya plume species ratios to the entire Central American arc gives mean HCl and HF fluxes of 1300 and 170 Mg day � 1 and a particulate sulphate flux of 40 Mg day � 1 for 1997 to 2004, although without further understanding of the degassing processes and sources at depth of these different volatiles, these arc-scale estimates should be treated with caution. Combining our arc scale mean SO2 flux with published measurements of volcanic gas compositions with respect to CO2 and H2O allows us to estimate mean CO2 fluxes of 4400-9600 Mg day � 1 and H2O fluxes of 70,000-78,000 Mg day � 1 for the arc. Preliminary comparisons of these estimates of outgassing rates with published volatile input fluxes into the Central American subduction zone, suggest that Cl is more efficiently recycled through the subduction zone than CO2. The results for H2O are inconclusive. D 2005 Elsevier B.V. All rights reserved.

Volcanoes have only recently been recognized as a potentially major source of reactive bromine species to the atmosphere, following from the detection of bromine monoxide (BrO) in the plume emitted by Soufriere Hills Volcano, Montserrat. However, BrO is not expected to be emitted in significant quantity from magma, presenting a puzzle regarding its formation. We report here new field measurements of the tropospheric plume emitted by Mt. Etna, Italy, which provide the first direct evidence of fast oxidation of halogen species in a volcanic plume, and lead to an explanation of how BrO is generated from magmatic HBr emissions. We show that the timescale of BrO formation (a few minutes after emission into the atmosphere) is consistent with rapid heterogeneous halogen chemistry involving sulphate aerosol in the plume. The model highlights considerable complexity to the oxidative chemistry of volcanic plumes.